Dye from thio-oxazolediones



oct. 24, 1939. G, s, BROOKER- 2,177,401

DYE FROM THIO -OXAZOLEDI ONES Filedb Aug. 13, 1936 NoLYL/nfn -T OxAzoLeD/ONE `zzo mamyl ZO 56 40 44 48 52 5b 60 640 III/.L

wom/L IN VENTOR:

BY n- 50 mulas:

Patented Oct. 24, 1939 DYE FROM Tmo-oXAzoLEpIoNEs Leslie G. S. Brooker, Rochester, N. Y., assigner,

by mesne assignments, to 4Eastman Kodak Company, Rochester, N. Y., a corporation of :New

Jersey Application August 13, 1936, SerialNo. 95,927 In Great Britain November 15, 1935 15 claims. (C1. 26o-240) lThis inventiony relates to dyes from thiofoxazolediones. More particularly, this invention relates to merocyanine dyes from thio2,4(3,5) oxazolediones and to` a process for preparing the 5 saine.r yThese new merocyanine'dyes serve to altertlie@sensitivity of photographic emulsions.

This application is a continuation-impart of my copending application, Serial No. 752,036,

' led November 8, 1934 (now United States Patv ent 2,078,233, dated April 27, 1937)k Which is in turn a continuation-impart of my copending application, Serial No. 739,502, filed August 11,

, 1934. In my copending application Serial No.

752,036, are described photographic emulsions vcontainingr photographic sensitizingdyes characterized by the following grouping:

whereinlA represents a divalent atom, such as Aoxygen or sulfur, n represents a positive integer, vR.represents an alkyl group, the-carbon atom Cifandthe nitrogen atom are situated in a heterol'cyclic ring system and the carbon atoms C2 L25 and C'a are situated in `another heterocyclic ring system. Inmy copending application Serial No. ,752,036-these kdyes lare referred to as N-alkyllheterocycl3`zlidenle,r N alkyl heterocylylidene ve'thylidefne 'and N,,alkyl-heterocyclylidene-butenylidene lderivatives yof heterocyclic compounds containing a reactive' methylene group, depending'up'on'iwhether n `represents 1, f2or 3 etc. It recently been `proposed to refer to this new clfassvoffidyes under the name merocyanine. Accordingly, when "nQin the above formula l-rep- TeSentsOne, the dyes are conveniently referred tor` as ,fsimple mero'cyanines', when n represents two, as merocarbo'cyanines and when n represents vthree ras merodicarbocyanines, etc;

Mycopending *application Serial No. 752,036 describes sp'eciii'cally photographic emulsions containing simple merocyanines, merocarbo- Vcyariines and merodicarbocyanines derived `from -rhodanines,- 5-thiopyrazolones, 2,4,6-triketohexahydropyrimidines and 2 thionaphthenones (thioind'oxyls). The instant application is directed to mei'ocyanine' dyes `from thio-2,4(3,5) oxazolediones; 'These new merocyanine dyes can be represented bythe ,following general forphenylene group, n represents a positive integer not greater than three, R represents an alkyl group, Y representsthe.non-metallic atoms necessary to complete a ve-membered or six-memberedheterocyclic nucleus, such as an oxazole nucleus (for example oxazole, benzoxazole or naphthoxazole), atthiazole nucleus (for example thiazole, benzothiazole or naphthothiazole), a selenazole nucleus (for example selenazole or benzoselenazole), a thiazoline nucleus, a selenazoline nucleus, a quinoline nucleus, a. benzoquinoline nucleus or a pyridine nucleus and Z represents the non-metallic atoms necessary to lcomplete ya =thio2,'4(3,5) -oxazoledione nucleus.

These newy .simple merocyanine dyes, where n represents one, can be prepared by condensing a cyclammonium quaternary salt, such as an oxazol'efa'thiazole, a selenazole, a thiazoline, a selenazoline, a pyridine or a quinoline quaternary salt `containing a mercapto group in the alpha or gamma position, i. e.y one of the so-called reactive positions, with a thio-2,4(3,5) -oxazoledione, containing a nuclear reactive methylene group, i. e., a. nuclear methylene group adjacent to la nuclear carbonyl or thiocarbonyl group, advantageously in the presence of a basic condensing agent. The reaction can be illustrated by reference to the specic condensation of 1- phenylthiobenzothiazole ethiodide with Z-thio- 2,4(3,5) -oxazoledione in the presence of triethylamine.

.condensing .agents such as `sodium carbonate or potassium .hydroxide can be used. cele'ratesv the reaction.

Heating ac- The follow-ingl examples serve to illustrate the procedure employedin. preparing lth'ese new dyes where n represents one. "Howeverg'I doi not intend that these examples limit my invention.` EXAMPLE 1.-3ethyl5 (i2-ethyZ-1-benzothiaaylithiazole ethiodide and 0.35 g. (1.05 mol.) were heated on the steam bath under. reflux'for' about minutes with absolute ethyl alcohol (15 cc.). The dye separated from the cooled reaction mixtur-e. After two recrystallizations from glacial aceticfaciditwwas obtained as pale yellow crystals=having a.:rn elting'point of 246-2489 C. The dye caribe represented by the following formula:

:2-thio2,4(3,5)oxazoledione, 0.9 g'. (1 mol.) 0f anhydrous' sodium acetate and 25 cc. of acetic anhydride. -This mixture was heated to boiling for` 5 minutes. On cooling yellow crystals separatedA out. rAfter two recrystallizations from glacial vacetic acid, thedye was obtained as pale yellow crystals melting at l94-197 C. with decomposition.

0.7 g.v (1 mol.) of 3-ethyl-2-thio-2,4(3,5)#oxazoledione, 2.0I g. (l mol.) of 2-phenylthio-quinoline ethiodide and 0.53 g. (1.05 mol.) were heated on the steam bath under reflux for 15 minutes with absolute vethyl-'alcohol (20 cc.)k The dye separatedA from` the cooled .reaction mixture. After two recrystallizatons .from methyl.` alcohol, the dye was obtained as orange'prisms having a melting point of 20L-202 C.

2-mercapto--naphthoxazole was prepared by heating on the steam bath 9.8 g. (1 mol.) of 1- amino-2-naphthol hydrochloride with 19.0 g. (excess) of carbon disulde in the presence of 5.0 g. (1. mol.) of triethylamine and 16 cc. of pyridine for about 24 hours. The excess carbon disulfide was then distilled off and 'water was added tothe reaction mixture to' precipitate the product. After recrystallization from methyl alcohol, the 'rrierca`ptof1- compound was vobtained vas-white. crystals, melting at: 26S-264 C.y

-T;.2-m-ethylthio--naphthoxazole was prepared by heating on thesteam bath'20.1 g. V(1 mol.) of 2-rnercapto--naphthoxazole.vwith,17.7 g. (1.25 mol.) fof. lzmethyl iodide in. a VSolution of l6.6 g. -(1 mol.) of potassium'hydroxide/(85%)..in absolute ethyl alcohol for abouti2'l5hours.. :The alcohol was vdistilled off and the, residue extracted with ether. The ether solution .'vlwas ,dried `and upon' evaporation yielded" the 'methylthio derivative as an oil. This wasdistilled under ref "duced pressure (3 mm.) giving a yellow distillate which solidiedpn standing. After recrystallization from ligroin, the methylthio derivative was obtained *aswhite crystals, melting at 68-70 C. 1.08 g. (1 mol.) of 2-methylthio--naphthoxaZole and 0.63 g.f'(1 mol.) of'dimethyl'sulfate were heated onthe steam bath for about 2 hours. To this reaction mixture was added 0.73 g. (1 vmoli) of 3-ethyl-2-thio-2,4(3,5)-oxazoledione and 0.53 g. (1.05 mols.) of triethylamine and cc. of absolute ethyl alcohol, The whole was heated for about 10fminutes on the steam bath. The dye separatedv from the cooled reaction mixture.. After recrystallization from methyl alcoholfit was obtained as pale yellow crystals, melting at 18'7-189 C.-with decomposition. The dye can be represented by the following formula: 'l

ylthio,A -Vnaphthylthio, benzothiazylthio:v or 5fpyrazolony1thioA Instead offfthe mercapto derivatives of benzothiazole and quinoline quaterf nary salts,` mercapto derivatives of, other cyclammonium quaternarysalts can; be used, for example, alkylthio, arylthio or heterocyclothio de- A rvatives of thiazole, oxazole, `thiazoline, thiazole, naphthothiazole, selenazole, selenazoline, benzoselenazole or pyridine Quaternary salts. Such dyes anda proc-ess for the `preparation thereof are described in the copendingfapplication of Leslie G. S. rBroolrerand Rusfsell. `Van Dyke, Serial No.'29,917, iled` July 5,1-1935.

These new dyes, Awhere n represents rtwo,can be prepared vby condensing a cyclamr'nonium Quaternary salt, such as an oxazole, a thiazole, a thiazoline, a selenazole, a selenazoline, apyridine or a quinolline Quaternary salt,y containing a anilinovinyl group inthe alpha or gamma, i. e.,

one of the so-called reaction, positions, with a f,-

thio2,4(3,5) oxazoledone, 'advantageously in the presenceof an acid binding agent. action can be illustrated withparticularreference to the specific condensation of l-(-anilino- The re- 2.46.5) oxazoledione, in' the presence of -triethyl amine. r u

i/ 02H5 y Such a dye ,is Called 5-(2-ethyl#1benaothiazyli dene-ethylidene) -g2- thm-2,4 (3,5) r-oxazoledione i The acetylated -anilinoderivative canl be advantageously employed in condensations of this type. The reactioncan alsol be carried outvin the presence of other :strong organic ,bases such as ,piperidina or aninorganic base such asl sodiurn hydroxide or sodium carbonate. Sodium acetate can also bey used as condensing agent.

d Thefollowing examples serve kto villustrate the procedure employed in preparing these new dyes Where 'n represents two. However, -I ydo not v intend that these exampleslimit -my invention in any manner.

1.7 g. (l'mol.) OrZ-(-anilinovinyl) -thia'zoline methiodide, 10.6 (1' mol.) of 2-thio-2,4'(3,5)oxa zoledione' and 0.53` g. (1.05 mois.) of triethylamine Were reluxed in 200C.' ofabsoluteethyl alcohol for about 15minutes. The dye sepa.'- rated vrfrom the 'cooled reaction mixture. v'After two recrystallizationsfrom methyl` alcohol, the dye' lwas obtainedffasy orange broWngranular crystals. Thedye can be represented bythe'fol lowing formula: l

l gazgleethlodide and l1.06 g.1 1.05 mois.) ,offriethylamine 'Were' reiiuxedffor, about vl5' kminutes in absolute etllylalcoghrol (15 cc.) The dye sepaiatedwfrorn the'cooled'lrea'ction mixture. `After recrystallization fromacetic acid .the `dye was obtain'ednj as 'reddish-brown, crystals with pale blue; am f Y f zoledione,` 2.'2.g,.(1 mol.) of 1-(-acetanilidovinyl) -benzoxazole ethiodide and A1.0.6 g. (1.05 mols.) of triethylamine were refluxed in absolute ethyl alcohol (20 cc.) for 15 minutes. The dye separated from the cooled reaction mixture.

.After twov recrystallizations from glacial acetic acid, the dye .was obtainedas yellow-orange needles. The dye can be represented by the follow- 0.7 g. (.1 mol.) of 3-ethyl2thio2,4(3,5)-oxazoledione, 2.25 g. (1 mol.) of l-(-acetanilido- VinyD-benzothiazole ethiodide and 0.53 g. (1.05 mois.) of triethylamine were refluxed in absolute ethyl alcohol '(20 cc.) for about 15 minutes. The dye separated from the cooled reaction mixture. y' After two recrystallizations from glacial acetic acid, the dye was obtained as crimson ycrystals melting at 243-245" C. with decomposition.,

EXAMPLE 9.-,3-ethyl-5-(Z-ethyZ-I-benzoselenazyZidene-ethylidene) 2 thiO-2,4(3,5) oazole dione 0.36 1g. (1 mol.) of 3-ethyl2-thio-`2,4(3,5) -oxazoleione, l1.25 `g. (1 mol.) of Z-(-acetanilidovvinyl)-benzoselenazole ethiodide and 0.26 g. (1.05 mols.) of triethylamine were reuxed for about'15 minutes rWith absolute ethyl alcohol (15 cc.). The dye separated from the cooled reaction mixture. After two recrystallizations from glacial acetic acid, the dye was obtained ascrimson crystals melting at 21S-220 C. with decomposition. The `dye can be represented by they following formula:

se 1 a 2. N (IJzHs In a similar manner -anilino derivatives of thiazole, naphthothiazole, quinolin-e, pyridine,

etacuaternary salts can be condensed with thio- 2,41 (3 ,5) oxazolediones,. 3alky1thio2,4 (3,5) -ox- CzHs CuHaNHH-HI This dye.' is called?3eethyl45'4.(2 ethyl1-benzothiazylidene -.butenylidene) -2-thio -2-4 (3,5) -oxa- Zoledione. In carrying out this type of condensation vI have found it' advantageous to employ the acetylated w-anilino derivative. The w-ianilino-fybromo-Al-butadienyl .derivative can also be used. l The reaction can also be carriedout in the presence of basicy condensing agents such as sodium carbonateor sodium acetate and acetate anhydride. Heat accelerates the condensations.

The following example'serves tov illustrate the procedure employed in preparing these new dyes where n represents three. `'.However, I do not intend that this example limit my invention in any manner.

EXAMPLE 10.-3-e'thy'l-5- (Z-ethg/Z-l -Abenaothiazylidene-butenylidene) 2-thz'o-2,4(3,5) -orrrteole` dione l v1.2 g. (imei.) of 1- -acetaniudoALS-butadienyl)benzothiazole ethiodide, 0.4 g. (1 mol.) of

(1 mol.) of triethylamine were refluxed in 10 cc. absolute ethyl alcohol forabout'A 10 minutes. The dye yseparated from the cooled reaction mixture. After recrystallization from glacial acetic acid, the dye Was obtained as minute,l dark, shiny green crystals. The dye can be represented by the following formular,

In place ofthe butadienyl derivative of benzothiazole, the butadienyl vderivatives of benzoxazole, naphthothiazole, quinoline, thiazoline, .ben-v -zoselenazole or the like can be used.r l

These new merocyanine dyes show a novel sensitizing action inphotographic silver salt emulsions, particularly silver chloride and silver bromide emulsions. Accordingly, my invention is particularly directed to the customarily employed `silver halide emulsions. f However, the light-sensiitive material employed'in the'einulsions of my in` 'vention can be any light-sensitive silver Asalt alone or combined vwithanother light-'sensitive silver salt, such as a silver halide. My invention is further particularly directed to the customarily employed gelatin emulsions, gelatin vbeing the car-- rier, such as a cellulose derivative o`r a synthetic resin, which has substantially no desensiltizing effect on the vsilver salt, can be used.

The sensitizing effect of these new dyes will be illustrated with reference to gelatinofsilverchloride emulsions in the .caseof thesimple merocyanine dyes, since it is in these particular emulsions that these dyes are most useful] In'the case of the merccarbocyanine dyes thesensitizing effect will be illustrated with reference to gelatino-silver-chloride and bromide emulsions.l lThe merodicarbocyanines areV useful in either chloride or bromide emulsions. The sensitizing effects will all be illustrated using the dyes derived from 3falkyl-2thio-2,4(3,5)-oxazoledione, as these dyes are the most useful. In particular, the merocarbocyanine dyes derived from 3-alkyl-2- thm-2,4 (3,5)0Xazolediones are most useful and the illustrations will be directed to these largely in order to give the most useful information to thev art. Fig. 1 of the accompanying drawing depicts the range of sensitivity of a chloride emulsion containing 3-ethyl-5- (1-etlflyl-Znquinolyli-A dene-ethylidene) 2thio2,4 Fig. 2 depicts the rangeof sensitivity of a chloride emulsion containing 3-ethyl-5.. (S-methyI-Z-/thiazolinylidene-ethylidene) 2-thio-2A (3,5)oxazo ledione. Fig. 3 ,depicts the range vof sensitivity of a bromide emulsion containing 3-ethyl-5-(2- ethyl-l-benzoxazylidene ethylidene)-2thio-2,4 (3,5)oxazoledione. Fig. 4 depicts the rangeci sensitivity of abromide emulsion containing 3- ethyl 5-(2-ethyl 1 benzothiazylidene ethylifV dene)2-thio-2,4 (3,5) -oxazlolediene Fig. 5 depicts a bromide emulsion containing 3-ethyl-5- (27 ethyll-benzoselenazylidene-(ethylidene) -2-thio`-v 2,4 (3,5)- oxazoledione. l 'l Some of the herein disclosed dyes have small desensitizing effects, together with sensitizing eflfects in another range of the spectrum.

In the preparation of photographic emulsions containing these vnew dyes, it is only necessary to disperse, homogeneously and. uniformly, from about 5 to about 100l mgvofV the dyeor mixture I. of dyes in about 1000 cc. of the cwable emulsion,

-the concentration of dye being varied according to the type of light-sensitive saltwhich goes to make up the emulsion and according to the effects (3,5) oxazoledione.

used in the art of emulsionmiaking. To prepare a gelatino-silver-halide emulsion,' the following 10 to 20 mg. of dye per1000 cc.l of emulsion suffice L 65 procedure is satisfactorytkAyquantity of the dyeisy to producethe maximumjsensitizingeffect with the ordinary gelatino-silver-halide emulsions.

The vabove statements are yonly illustrative and not to be understood as limiting my invention in f any sense, as it will be apparent that these dyes theplateorjlm, upon' which the emulsion has been'coated,`in a solution of the dye in an approjlpriate solvent, although such a method is ordinarilynotto be preferred; Theclaims are iny'tended to cover any combination of these newu dyes with a photographic silver salt emulsion whereby the dyelexerts a sensitizing effect upon the emulsions ,as well as a photographic element comprising'ai support, ordinarily transparent,

` y upon whicl'frftheV liglites'ehsitivevr emulsion is; coated or spread and permitted to set or dry.V 4

The herein disclosed dyes, particularly the simple merocyanines and the merocarbocyanines, are

useful in therconstruction of light lters the, simple,xnerocyaninesabsorbing: light of thev shrter wavelengths and some ultraviolet. The merocarbocyanines are useful as coloring matters for textiles, particularly cellulose acetate silk or the like. The term dye as used in connection with the` simplea-rnerocyanines is a loose usuage as these substancaeoiten ofY a pale color.

It is to be understood that theshereinA disclosed `dyes probably exist intwo formswhich for one group of my new dyes can be illustrated as fol- As illustrated these forms are interconvertible one into the other, i. e., the forms are virtual tautomers'. y

` What I claim as my invention and desire to :be secured by Letters Patent of the United States of America is:

1. A dye characterized by a formula selected v from thefollowing two formulas:

wherein A represents an atom selected from the group consisting of oxygen and sulfur atoms, D represents a radical selected from the group oonsisting of vinylene and phenylene groups, n repre- Vsents a positive integer not less than two and not greater than three, R represents an alkyl group,

mula I group consisting of oxygen and sulfur atoms, n represents a positive integer ynot smaller than two and not greater than three, R represents an alkyl grouprY'representsthe non-metallic'atoms necessary tocompletef a heterocyclic nucleus selected from the group consisting; of ve-membered and six-membered heterocyclicnuclei and Z represents the lnon-metallic atoms necessary to complete a thio-2.4(3,5)-oxazoledione nucleus.

`3. A dyecharacterized by a formula selected from the followingx two formulas:

wherein Dre'presents' a radical selected from the group consisting of vinylene and phenylene groups, n represents a positive integer not smaller than two and not greater than three, R represents an alkyl group, Y represents the nonmetallic atomsnecessary to complete a heterocyclic nucleusselectedsfrom the group consisting offve-membered and six-membered heterocyclic nuclei andfZfrepresents the,- non-metallic atoms necessary. to complete. a thm-2,4 (3,5) -oxazoledione nucleus. 1 l

4- A dyejcharacterized byr the.l following formula:

I,YX zx R-iv-o'=(oH-cH) ,=-o`=o wherein ARHrepr'esents an alkyl group, n represents a positive integer not smaller than two and not greater than three,`V Y'represents the nonmetallic atoms necessary to complete a heterocyclic nucleus selected from the group consisting of five-membered and six-membered heterocyclic nuclei and Z represents the non-metallic atoms necessary torycompletey aAv ffthio2,f4(3,5) -oxazoledione nucleus.

5. A dye characterized by a formula selected from the following two formulas:

wherein R represents an alkyl group, Y represents the non-metallic atoms necessary to complete a ve-membered heterocyclic nucleus and Z represents the non-metallic atoms necessary to complete a thio-2,4(3,5) -oxazoledione nucleus.

7. A dye characterized by the following formula:

wherein R represents an alkyl group, Y represents the non-metallic atoms necessary to complete an azole nucleus andZ represents the nonmetallic atoms necessaryv to complete a thio- 2,4(3,5)oxazoledione nucleus. f

8. A dye characterized yby the following formula: o Y

wherein R and R represent alkylgroups and: Y

represents the non-metallic atoms necessary to complete a thiazole nucleus.

10. A dye characterized `ley the following formula: 1

wherein R represents an alkyl group. Y

11. A dye characterized by the following for- Amula:

l R--c'=oH-o11=c".-c|i=o n wherein R and R represent alkyl groups'and Y represents the non-metallic atoms necessary to complete an oxazole nucleus. 1,0 12. A dye characterized by the followingfcr.-v mula: f

wherein R and R represent alkyl groups. y

14. 3 ethyl 5 (2-ethyl-1-lcenzotlfiiazylidene ethylidene) -2-thio-2,4 (3,5) oxazo1edione.

15. 3 ethyl `5 (2 ethyl-l-benzoxazylideneethylidene) -2-thio-2,4 (3,5) oxazoledione. y

LESLIE G. S. BROOKER. 

